Process of separating sodium salts from mixtures thereof



Dec/15, 1931. w. ALLEN ET AL 1,836,426

PROCESS OF SEPARATING SODIUM SALTS FROM MIXTURES THEREOF 3 Sheets-Sheet 1 Filed Feb. 1, 1950 w, I/0/l/ wv w M w w m .3 Qi \w gax QQ 3 3% was Dec. 15, 1931. 'w. H. ALLEN ET AL 1,836,426 PROCESS OF SEPARATING SODIUM" SALTS FROM MIXTURES '1'I'IERE0] 5 Filed Feb. 1, 1930 3 Sheets-Sheet 2 Dec. 15, 1931. w. H. ALLEN ET AL 1,836,426

PROCESS 01f SEPARATING SODIUM SALTS FROM MIXTURES THEREOF Filed Feb. 1, 1930 3/ Sheets-Sheet 3 Grams 0/ #0 130 per /00 firams of wafer 8 G p k V I e 1 /0 2a 50 I 40 50 v Grams of M1 00 per /00 Grads of Walter Patented Dec. 15,1931

" UNITED STATES PATENT. OFFICE WII-LIAI K. 5.14m, WILLIAM A. GALE, AND CHARLES 1'.

AMERICAN POTASH & CHEMICAL COBPQBATIONT, MFA,

T101! 01' DELAWARE roman, assreuons TO CALIFORNIA, a 00 .20 I

mean, or mom. cm-

success or SEPABA'I'ING somuu sam's not mx'ruans m0! Application ma February 1, 19:0. Berial at. 488,208.

- This invention relates to new and useful methods for, separating and/or sodium carbonate rand/or sodium chloride from admixture or combination with 5 each other either alone or in the presence of other salts. Such complexes may exist either in the form of solution as in the'ca'se of various natural or artificial brines, vor in the solid state, as in the case of the doublesalt m burkeite (Na CO 2Na SOQ, or of cal mixtures of the Various salts.

In the evaporation and manipulation of hose of Searles and Owens brines such as t Lakes, California, for the recovery of borax mechaniand potash, large quantities of such sulphatecarbonate com lexes and mixtures are obtained and it is inthe utilization of these materials that the process of-this invention is of special value. an Application for ent, Serial Numbers 308,496 and 309,27 9, filed v September 26, 1928, and September 29, 1928, set forth methods andeciwipment by which various sodium salts may precipitated and g5 separated from suitable mentioned processes produce from Searles Lake brine sodium chloride, containingsmall amounts of carbonate and sulphate of sodium. Those processes also produce a sul- 3o phate-carbonate complex, containing small amounts of sodium chloride. A sulphatecarbonate complex called burkeite, having an approximate formula Na GO,.2Na,SO,, 1s

produced from Searles Lake brine. Like- 7 wise other sulphate-carbonate complexes,

- such as 2Na CO,.3Na,SO,, may be precipitated from such brine during evaporation.

While the former double salt .has been termed burkeite in past literature, we wish 40 to include in this classification other similar complexes, such as the last mentioned complex, which are similar in their characteristies with the true burkeite and may be true double salts or mixed crystals.

In addition to such complexes,

continued sodium sulphate aforementioned applications for invention. I

In the past no satisfactory method has been separation of so- United States Letters Patbrines. The aforethe addition of ammonia,

' tration is several high temperature evaporation of Searles Lake, Owens Lake and similar brines results in the precip'tation of a certain amount of phate salts together with a small amount of sodium chloride tial degree from ride, precipitated during evaporation of brines, by the processes and equipment 0 United and resimilar such States Letters Patent. The refinin covery of pure salts from these an mixtures is one of known for the economical dium sulphate from such sulphate-carbonate complexes which would be suitable for use As a result, such ma;-

terial, produced as a byproduct in the borax. been discarded as on a'commercial scale.

and potash industry, as waste. Various methods of treatment have been suggested: for example, the fractional and successive precipgation of sodium 811 phate and sodium car nate from has been propose However, such a process is found not to be operable due to the formation and precipitatron of the double salt burkeite, which has the presence. of amv a very low solubility in monia; 'In order to precipitate sodium carbonate from a sulphate-'carbonateffcomplex by cooling it is necessary that the ratio of carbonates to sulphates be vexg 22531, and also, the actual concentration 0 'um'sulphate be very small. It is therefore another object of the present invention ,to'provide a process for manipulating sulphate-carbonate com lexes and/or mixtureswhich is capable of c anging the ratio of carbonates to sulphates in solution so thatthe resulting carbonate concentimes that of the sulphate concentration; so-that a solution is obtained.

sodium carbonate monohydrate (Na CO .H O). These carbonate and sulare separated toa substanthe bulk of the sodium chlothe the objects of the present solutionby i or by saturation with ammonia, i

- the raw materia having a low. sulphate concentration, suitable for precipitation of sodium carbonate by cooling alone or through the use of ammonia or carbon dioxide gas.

Other objects of the invention will become apparent from the following exposition.

The process of the present invention is in part, at least, a cyclic process and the point at which the process starts is dependent in part upon the nature of the raw material, i. e. the ratio of sulphates to carbonates in and further, upon whether the sulphate-carbonate complex to be treated contains an appreciable content of sodium chloride.

In case of. sulphate-carbonate mixture or a complex such as burkeite, having a greater ratio of sulphate to carbonate than that of a solution at the point saturated with burkeite and the dekahydrates of the two single salts and containing little or no sodium chloride, the first step of th manipulation of the complex or mixture with water in the Glauber salt (Na SO .10H O) field, in order to precipitate this salt. The

manipulation is preferably conducted by dissolving the complex in water at a temperature below. the transition temperature between Glauber salt, sal soda and the double salt burkeite, suflicient of the complex being added to exceed the saturation point of the Glauber salt with a result that this salt is precipitated, thereby increasing the ratio of carbonate to sulphate in solution. Sulficient of the complexis added to increase the ratio of carbonate to sulphate in solution in excess of that which exists in burkeite or similar complex, and preferably suflicient to arrive substantially at the point of saturation of sal soda (sodium carbonate de'kahydrate), and of course, Glauber salt.

The resulting solution will be hereinafter described as the cold sulphate liquor for the purpose of identification regardless of its method of production. This step of the process is valuable as applied to all complexes or mixtures, substantially free of sodium' chloride, the ratio of carbonate to sulphate of which is less than, or only slightly greater than, unity.

Preferably the operation is conducted at that temperature suitable for causing the mixture in this operation to substantially reach the transition point between burkeite, sal soda, and Glauber salt. This step of the process may be employed upon complexes which have a carbonate-sulphate ratio greater than that of burkeite, but less than that corresponding to the said transition point.

It is also possible to eflect a partially equivalent operation through mani ulating the complex in the lower part of the an ydrous sulphate field by dissolving the complex ata temperature just above the transition temperature between the anhydrous sodium sule process consists in phate and Glauber salt. When this is done, by an addition of an excess of the complex to water, sufficient to exceed the saturation point of the solution with respect to the anhydrous sodium sulphate, anhydrous sodium sulphate may be caused to precipitate until the solution reaches a pointof saturation with respect to burkeite and anhydrous sodium sulphate. The ratio of carbonate to sulphate may be thus increased, starting with any mixture or complex of sulphate and carbonate whose ratio of carbonate to sulphate is less than that of a solution saturated with respect to burkeite and anhydrous sodium sulphate at the temperature employed. However, when operating in this field, the in crease in the ratio between the carbonate and sulphate which can be secured is less than that which can be secured when operating in the Glauber salt-field. Moreover, the process is slow in the anhydrous sodium sulphate field, while it is a rapid process in the Glauber salt field.

The next operation in the process is the heating of any solution of such composition as obtained on separation of Glauber salt from the first operation, i. e. the cold sulphate liquor. With less advantage and efficiency this operation may be applied for increasing the ratio of carbonate to sulphate of many solutions-or materials in which the ratio of carbonates to. sulphates is greater than that sufficient amount toessentially saturate the Y solution withthis salt at the temperature to which it has been heated. J ustsulficient common salt is added to reach saturation, so that no sodium chloride will remain undissolved. The order in which the heating and the addition of sodium chloride is carried out is immaterial and both may be done simultaneously. The effect of the addition of sodium chloride is to greatly decrease the solubility of burkeite. Accordingly, this salt (N a CO 2N a 80,)

is precipitated from the solution to such an extent that only a small amount of S111- phate remains in the mother liquor. The burkeite precipitated in this step is separated from the hot liquor and may be utilized in the first step for retreatment either by itself or, together with a fresh batch of material. The resulting hot liquor is termed hot carbonate liquor for further reference, the term applying to any such liquor saturated with sodium chloride and burkeite, having a high '35 at this point, yielding assume place of sodium chloride to the heated solution in suflicient quantities so that its sodium chloride content will saturate the solution. The burkeite content of the impure common salt will be precipitated or remain undissolved alongythe burkeite precipitated from the solution itself.

The hot carbonate liquor, after separation from burkeite contains a high ratio of carbonate to sulphate, and very little of the latter. In this condition, it may be cooled until it becomes saturated with respect to sodium carbonate dekahydra-te or heptahydrate. This cooling to the point of saturation may cause the precipitation of a small quantity of pure sodium'chloride, which may be separated a valuable commodity for commercial use, or for use in the cyclical rocess. After the removal ofsodium chloride, the solution may be additionally cooled, precipitating sal soda until the point of an saturation w th Glauber salt isreached. By

' wise the solution may N8,SO4N8.2 between 0 C. and 100 C.

.Figure 2 the 50,

such a' process a lar yield of pure sodium carbonate is attaina le. The solution also, usually after slight dilution may be used to monohydrate the addition of ammonia, instead of the final cooling operation treated with carbon dioxide gas for the removal of the carbonate content thereof. y

' The process of the present invention will best be understood from the description of a referred form or example of the process emg the invention, the being descri in connection with e accompanying drawings, in which F' 1 is a polytherm representing the solubility and base relations for the system- ,0, at all temperatures Figure 2 is a polytherm of the same sys;

tem,

saturated with sodium' chloride. In

Figure 1 has been superimposed in orderto better show the efiect of sodium .chloride on the solubility of burkeite.

' Figure 3 1s a diagram of the isotherm 'a-b-d-e together with the same isotherm-- when saturated with sodium 1 "s P chlor de and the 25 C. isotherm hE-k from Figure 1C V Referring first'to Figure 1 of the drawings there is re resented in the pe 've=a polyphate, sodium them of t e system'sodium carbonate and water, upon the outer surfaces or fields of which there is indicated the p'arthe composition of burkeite, Na CO QNa S 'ust specified. Likebe of common salt together with a two fields represe ts the field of existence of solutions saturated with two adjacent phases.

The intersection offthree boundaries repre sents the composition of the liquid phase of the invariant system containing the three adjacent solid phases. Thus in Flgure 1 the line A-B represents all solutions saturated with the two salts Na,SO,.10H O and Na CO .10H,O, while the int B re resents 'the composition of the so ution at t e temtransitlon of the two single perature of hydrated salts to the anhgdrous double salt The efiect of sodium chloride on the various solubilities and transition temperature is obviously seen from a comparison of Figures 1 and 2. For

example, the point B in the absence of sodium chloride and'other impurities is at approx1- mately 26 0., while in saturated sodium chloride solution the temperature of this transition point is approximatel 15 C. We are aware of the fact that the ekahydrates of both sodium carbonate and sodium sulfate tend to form a limited series of mixed crystals while separating fro solutions containing both salts. However, we have found that this tendency is so slight that it does not cause any serious contamination of the single salts, and'therefore has no appreciable eflect on the usefulness of our invention.

In the preferred process we employ salt mixtures consisting of what are termed salt trap salts and clarifier salts. ,The former contain about 60% sodium chloride, 20% sodium sulphate and 10% sodium carbonate, while the latter contain about 40% sodium sulphate, 35% sodium carbonate and 10% sodium chloride, being water and insoluble matter.

The sothe remainder in both cases called salt trap salt comprises a mixture small amount of sulphate-carbonate complex similar to burkeite. I v

Olarifier salt contains a large proportion of the. sulphate-carbonate complex t ther with small ainountsof common saltan some sodium carbonate monohydrate. The presence of this small quantity bonate monohydrate is very desirable in the final production of the hot carbonate liquor.

At this point we .have an alternative regardingthe prime treatment of such mixture as k a satisfactory cold sulphate liquor, it s requisite that little or no sodium chloride be resent. Hence, it is nry to remove from the raw material Employed in the first step of the process the example, by leaching. Said leaching may be done with water,

of sodium carerein descri In order to produce 7 or it may be accomplished lum chloride; for

ing from that liquor the hot carbonate liquor. For most eflicient results with the latter process, it is preferable that the raw material, so leached, should contain sodium chloride in amounts equal to or less than that re uired for the saturation of the cold sulphate iquor in the production of the hot carbonate liquor.

If a raw material does contain sodium chloride in excess to that required, it may be given a partial leach with water to reduce the sodium chloride content to the desired value. either prior or subsequent to the treatment resulting in the production of the hot carbonate liquor. 'i a Since the process of this invention is, in part at least, cyclical the following example will be set forth as starting at a point where there is available a sodium sulphate-carbonate complex, substantially freed from sodium chloride. Said raw material was produced by leaching clarifier salt and contained approximately 34% Na CO and 66% NA SO, on a dry basis.

of Water and stir the mixture while maintaining the temperature at 2225 C., or at a temperature closely approximating that of the transition point B, although preferably operating slightly under this point.

In practice, the operation of the present-invention is cyclical and considerable burkeite,

resulting from the production of the hot carmeans must be used for'cooling the solution,

since the process evolves heat. The amounts of water and salts chosen are such that upon the solution reaching the composition E; that is, saturated with Glauber s'altand substantially saturated with sal soda, all of the complex will have been dissolved. E, which is generally chosen as approximately at the point B, although slightly below the same, the solution has reached saturation with Na CO .10H O. During this pr0cess Glauber salt, weighing approximately 825 pounds is precipitated and is filtered or from the solution, saidotherwise separated.

' the cold, sulphate liquor.

.This salt is given a slight wash with cold water and then contains little sodium carbonate or otherimpurities. The cold sulphate liquor which weighs essentially 1890 To, for example, 1000' pounds of this complex, we add 1,721 pounds.

After reaching a a salt separates while At the point pounds has approximately the following composition Naoo.

N312 S 0. 1:11:11: I I I I Water-a Pounds 340 296 The cold sulphate liquor'is then heated to some suitable temperature so that the composition of the solution is within the burkeite field. The exact temperature of heating is dependent upon the quantity of sulphate which will be permissible during the subsequent steps of recovering sodium carbonate; the higher the temperature of heating, the lower the sulphate content of the resulting hot carbonate liquor, and, likewise, the greater the heating the greater will be the yield of pure sodium chloride produced.

However, excessively high temperature of heating lowers the carbonate content of the liquor, thereby decreasing the quantity recoverable from a given quantity of liquor in subsequent operations. Also, excessive heating may cause theprecipitation of sodium carbonate monohydrate from the liquor, v which however may be redissolved by the addition of water.

We have found the temperature of 50 C. to be-satisfactory for the process herein described. The-heating operation causes the solution to follow the line EF in Figure 1.

The solution is then brought to saturation point near G on. the point the solution is saturated with sodium chloride and burkeite and nearly saturated 105 with respect to sodium carbonate monohydr'ate.

This operation precipitates burkeite, pro-' ducing from cold sulphate liquor the hot carbonate liquor of the following composition: no

. Pounds N31200:; Na SO 32 N aCl 327 Water 1260 The precipitated burkeite weighs approximately 361 pounds and is filtered off from the solution and returned to step. 1 of the" process to be retreated together with-a fresh batch of material, (e. g. with leached clarifier salts). The hot carbonate liquor is then further treated for the recovery of'the sodium carbonate and tents, as hereinafter described.

The process is commenced with 1000 pounds of the complex, while 360 pounds of burkeite are recrystallized and returned. Thus, only 396 pounds of anhydrous sodium sulphate are consumed and there are recovsodium chloride conered 825 pounds of Glauber salts containing 7 ust clarifier salt or simi inratio not exceeding 2.7 to one;

364 pounds anhydrous sodium sul hate. This represents a net recovery of Na, 4 of ap roximately 92%.

n the just described process, in place of saturatin the solution at the point F with pure sodium chloride, itis advantageous to employ salt tra salt of the composition supra, using su cient of this salt trap salt to supply the required 327 pounds of sodium chloride essential to saturate the solutlon. By so doing, the carbonate and sulphate content of the salt trap salt is purified of chloride and recovered for use in the procem. The carbonate and sul hate content of the added salt remains un issolved and is present with the precipitate of burkeite from the solution, whichis returned to the cyclical process.

While impure sodium chloride, such as salt trap salt, is advantageously employed in the production of the hot carbonate liquor, as

described, even greater advanta e accrues from the use of clarifier salt, 0 composition supra. The requisites for gaimn this added advanta e in toto are that sai %ar. mixture .should concarbonate it should preferably contain jfree sodium carbonate, and itshould contain not more than sufiitainsodium sulphate and'sodium "cient sodium chloride to saturate the liquor as hereinbefore set forth. Asa matter of fact, clarifier salt fulfills these requirements.

In this .variation of the present invention,

which is a highly preferred form, the whole ofthe cold su phate liquor produced is mixed with all theclarifier salt available, said clarifier salt supplying the major 3 Sufficient salt'trap salt, or other ortion of the the fprocess. orm of sodium chloride is added to sup iiy thereuisite saturation with respect to t e mixture is heated, as described.

Due to the presence of carbonate monocomplex utilized in step 1 o hydrate in clarifier salt, the resulting hot 5 carbonate liquorreaches point-n,

-' saturated with Figure 3,

sodium chloride, sodium carbonate monoh drate and burkeite,'and consequently contains more sodium carbonate and p less sodium sulphate than the previously described liquor at point complex content of the clarifier salt remains undissolved, since burkeite is precipitated by virtue of the heating and salting out treatment of the cold sulphate liquor.

If an excess of sodium carbonate monoeffect its complete solution, producing a hotcarbonate liquor essentially saturated with sodium chloride, burkeite and sodium carbonate .monohydrate at the temperature emaCl; and

G.. This is very de-- sirable. The burkeiteor sulphate-carbonate w The excess of carbonate-sulphate and burkeite is then filtered out and to the cyclical process for the proployed. complex returned duction of sodium sulphate and the cold s111-' liquor of maximum value and simultaneously Y providing the desired raw material for the rst step of the process.

While it is possible (and we have done so in the past) to em loy water for the removal of sodium chlori e (and sodium carbonate monohydrate together with small amounts of the complex) from the clarifier salt, subsequently adding this leach liquor to the cold sulphate liquor prior to the heating and salting-out step, the combined procedure just described is preferred as it simplifies the process and insures the production of the optimum hot carbonate liquor.

If it is found after the above treatment liquor that the resulting preci itated burkeite and undissolved sulphate-car nate com lex contains residual sodium chloride, said so ids, after removal from the hot carbonate liquor, may be subjected to appropriate treatment with water for the dissolution of the undesirable sodium chloride. This may be accom plished' by means .ofsuflicient washingwith substantially free of sodium chloride, con- 'taining inore sodium sulphate than sodium carbonate, isdigestedfat or -below the temperature'of the transition point of the dekahydrate of sodium sulphate and sodium carbona'te to the 'double salt burkeite. The resulting solution contains more carbonate than.

sulphate and the excess sodium sulphate therefore precipitates in the form of Glauber salt or remains as an undissolved residue, depending upon .the form in which it occurs 1n the original material. The net result is a solution containing essentiall all the carbonate and part of the sulphate o the material with "of clarifier, or like salty-with cold sulphate I Ill any soluble impurities that may be present,

- while the solid phase represents practically pure sodium sulphate salt.

The solid Glauber salt, foregoing example, is filtere in the form of Glauber (produced in the ofi, washed free I of mother li uor and maybe marketed as such or maytreated for the production of anhydrous sodium sulphate. For example,

- Glauber salt may be dissolved in a minimum Less sodium of water at or near the temperaure of maximum solubility which is approximately 324 C. for the pure solution (see Figure 1). The resulting saturated solution of sodium sulphate may then be evaporated at any temperature above the transition triple effect evaporator, for instance, and pure anhydrous sodium sulphate precipitated. Such precipitated anhydrous sulphate is separatedfrom the mother liquor by any suitable means, such as a continuous vacuum filter or a centrifu 'al. The mother liquor is suitable for further processing of Glauber salts. M

The product is suitable for the market as obtained.

The saturated solution of sodium sulphate may be treated with ammonia gas for the precipitation ofanhydrous sodium sulphate. To this end ammonia gas is caused to distil into and be absorbed in the solutiomrresulting in the precipitation of the desired salt. After removing the precipitate, dium sulphate therefrom, the residual liquor is heated and boiled forthe recovery 'ofi'the dissolved ammonia, the same being utilized for the further precipitation of sodium sulphate from con centrated sulphate solution while the residual liquor may be used in part for further dissolution of Glauber salt.

While the foregoing methods produce a .very satisfactory product, the expense of heating, boiling," nd evaporation is somewhat undesirable. In keeping with the precepts of the present invention which provides means for the simple recovery of several sodium salts from mixtures thereof with the least possible expenditure of energy, we prefer the following mthod of anhydrous sodium sulphate production.

Glauber salt is dissolved to saturation in,

water at 32-35 C. To this solution we add sufiicient salt trap salt (or any other suitable mixture high in sodium chloride and containing sodium sulphate and little sodium carbonate) to essentially saturate the solution with respect to sodium chloride. This treatment serves to precipitate the greater portion of thesodium sulphate as the anhydrous salt. chloride may beadded than is necessary to produce complete saturation of the solution, in which case the recovery of the anhydrous sodium sulphate will be somewhat reduced; but, the purity, in case the sodium chloride employed is badly contaminated, is materially increased.

. For example,; to 1150 pounds of Glauber salt, containing 510 pounds of N a SO,,--there is added 360 pounds of water, providing a total of 1000 pounds of water, I brought to 35 C.,or slightly higher. The resulting solution may be filtered or settled for the removal'of insoluble matter, if desired.

, To this solution there is added 460 pounds of dry salt trap salt of composition supra conpoint, in a ing-out processes may mo'st any mixture of pounds Na SO and 51 pounds N a CO The mixture is stirred for 35 C. and the solid residue recovered on a suitable filter. The resulting crop of anhydrous sodium sulphate weighs 524 pounds, dry basis, and after having been given a slight displacing wash with water is essentially free from impurities, containing less than 1% N aCl and 1% Na CO -While the use of pure sodium chloride or the aforementioned boilbe employed, the advantages of the preferred process are obvious.

ore sodium sulphate is recovered than is introduced as Glauber salt, the excess as well as that required to saturate the solution being obtained from the impure salt employed. Further, the presence of the small amount of sodium carbonate reduces the amount of sulphate which will remain in the mother liquor as compared with the case when employing pure sodium chloride. Furthermore, the small amount of carbonate reduces the quanti ty of sodium chloride needed to saturate the solution. The efficiency of the above process is further increased by decreasing the quantity of water employed for dissolving the Glauber salt: in which case, the quantity of common salt employed is adjusted so as to' superior for many purposes to the socalled salt cake of commerce, being free of acid and iron compounds.

Another variation of the above process consists of saturating the Glauber salt solution with respect to sodium chloride at a high temperature, say -100 C. At these temperatures, anhydrous sodium sulphate is even more insoluble than at 35 (3., thereby affording a greater yield of that salt. After removing the anhydrous sodium sulphate, the

liquor may be cooled to 35 C. or slightly lower, and a crop of pure common salt recovered. By this method an improved yield of anhydrous sodium sulphate is recovered and a crop of pure sodium chloride is produced from the contaminated raw material. Said salt may be filtered from the liquor, washed, dried, and sold as table salt of high quality.

While the process, so far, has been described asapplied to solid raw materials containing more sodium sulphate than sodium carbonate, the process may be applied to alsodium carbonate and sodium sulphate, tamination with sodium chloride, such mixture existing either as solids or as solutions. In certain instances, the first step of the process may be omitted entirely, and the cold sulphate liquor or hot carbonate liquor produced by direct treatment. Any mixture or about a half hour at I. complex of carbonate and sulphate, essentially free of sodium chloridecontainingmore I with so ium chloride, may preclpitate burkecontaining which. residues contain sodium carbonate in excess of the sodium sulphate, may be em- .step.

. soli complex or mixture containing carbonate than sulphate rhust contain.

sodium carbonate, uncombined with comficient to remove it sludge from the and sodium chloride may be added'thereto, in order to dissolve fri 'cipitated, for this purpose. It will be seen ite and assume a composition as represented by variation from approximately point G to point n of 'Figure 3. said solution being saturated with sodium chloride, burkeite and saturated or nearly saturated with sodium carbonate monohydrate at the particular temperature employed. Complexes or mixtures of sodium carbonate and sodium sulphate, the former in excess of the latter and likewise containing sodium chloride, which will, upon being brought to saturation, approximate the hot carbonate liquors represented. by points from G to n of line m-n of Figure 3 or points intermediate between the same and points E and Z, respectively, which upon complete saturation with sodium chloride will fall at or near points G or n, may likewise be utilized directly for the production of the hot carbonate liquor.

Solid residues resulting from the saturation of cold sulphate liquor with sodiuin chloride,- (said process beingcarried out hot),

ployed as aforementloned for the production of the cold sulphate liquor by direct dissolution.

However,b we have found that-unless the ratio of car onate to sulphate in the chloride free residue is well over a fixed value, as specified below, it is not most economical or ,ef-

, from. the leaching step and to subject the same to a direct dissolution It is preferable in such instance to dissolve up as .much aspossible of the excess carbonate remaining in such chloride free slud This is based upon the factthat any more free lexes; Hence, rior to the removal of the each step, additional water the carbonate and arrive at a int saturated with respect to sodium chloride, sodium carbonate monohydrate and burkeite, simulating point n of Figure 3, for the articular temperature employed.

ile fresh water may be .used for this pur se, we have found it advantageous :to emp oy the mother liquor from the final reration step, in which sal soda is pm from the following description that such liquor contains certain residual values of so-' dium carbonate which ma advantageously be added to the system at t is point.- p,

\ C; resultin solution, when heated and saturated '-bonate liquor by lowing composition:

Even larger yields ride certain other natural brines,

essentially the same and changes made only inthe relative amounts of sodium sulphate,

sodium chloride and sodium carbonate recovered. The process of this invention is applicable to the separation and refining of one or more of thepthre e salts from almost any of an infinite number of combinations of the same, either in the solid state or in concentrated'solut-ion. The basic principles of the process, as herein set forth in detail and by solubility diagrams, comprise the essence of the present invention. The details for treating various mixtures for the production of the desired products and/or solutions therefrom are too numerous to list.

in detail, due.to the multiplicity of possible starting combinations or raw materials; but,

the basic principles of the process are set forth herein clearly and'in such a manner that one skilled in the art may make use of the same.

Along the line direct means as just described, we wish thereof as applied to the recovery of values from certain natural brines, containing carbonate, sulphate and chloride of sodium. Such process likewise comprises a suitable method for reducing burkeite, from which sodium sulphate and sodium carbonate may be produced, aslrerein described.

In treatment. f Owens Lake brine, approximately 141 gallons or 1529 pounds of brine is taken which of producing the hot carto set forth an example has essentially the fol-I.

Per cent v by weight Pounds Nl O0 0 Nag-S04 4:- 5 NaCl 13. 1 200 Other salts 6.0 92 Water 65. 4 1000 Total .i 100.0 1529 This solution is heated to 75 C. or above, and 100 pounds of .sodium chloride added. The mixture is stirred until essentially; all

the sodium chloride .is dissolved, this amount of sodium chloride being essentially the cor-.

f rect amount which just saturates the soapproximately- .67

luttion. I In so doing, pounds of burkeite are precipitated. In this manner a crop of burkeite is recovered from which sodium sulphate and sodium carbonate may be manufactured as herein 'described. of burkeite may be ob.- tained by this sim and saturating .wit respect to sodium chlonotably 1c expedifiit of heating I Searles Lake brine. The hot brine resulting from this burkeite precipitation may be cooled for the separation of pure sodium chloride.

The residual liquor, in the case of the aforementioned Owens Lake brine, after filtering out the precipitated burkeite had the following composition:

Na CO N a SO N aCl Other salts \Vater Total 1562 It may be seen that the above liquor corresponds very closely to. the; hot carbonate liquor produced from solid salt mixtures. To be of value the hot carbonate liquor, saturated with sodium chloride, should contain Pounds 150 20 300 92 1000 a high sodium carbonate content and a low.

sodium sulphate content, it being understood that the higher the carbonate and the lower the sulphate, the more valuable this liquor will be in the subsequent steps for recovery of sodium carbonate. Liquor, resulting from the treatment of Owens Lake brine as shown above (but not that resulting from the precipitation of burkeite from Searles Lake brine), fulfills the stated' requirements. Hence, by this method, the desired hot carbonate liquor is produced directly from a raw material.

When a complex or mixture, substantially free of sodium chloride, contains 50% or more sodium carbonate in excess of the sodium sulphat e, then we find it advantageous to treat such mixtures in a manner quite similar to that originally described in connection with the production of Glauber salt but, in this case, recovering primarily, a valuable crop of sal soda. For example, to 1100 pounds of a com lex containing 62.5% N a CO- and 21.0% N a 0 the remainder being essentially water and insoluble matter, we add 1530 pounds of water. The mixture is stirred and maintained at 25 C. for an hour or so, means for cooling being supplied since the reaction is exothermic. In dissolving, the composition of the solution follows along line O-Y of Figure 3 to a point Y, saturated with respect to sal soda. The complex then continues to dissolve, increasing the sodium sulphate concentration of the solution and precipitating sal soda. A crop of the latter, weighing 1128 pounds, on a dry basis, containing 418 pounds of sodium carbonate, is recovered, representing a direct recovery of approximately 61% of the sodium carbonate introduced.

Just sufficient of the complex or mixture may be added to water to bring the resulting solution to'a point E. However, it may be preferable to stop such addition somewhat short of point E, say at point Z. The soluture of production.

with that Glauber salt tion of composition represented by point E is analogous to the cold sulphate liquor produced above, and may be so termed. Any solution having a composition between points Z and E on the line 7cE comprises a suitable cold sulphate liquor for the subsequent production of hot carbonate liquor. A solution of composition Z, when heated and saturated with sodium chloride, precipitates burkeite, traveling along the line Zn to approximately point n saturated with burkeite, sodium chloride and sodium carbonate monohydrate, which is the optimum composition for the hot carbonate liquor at its particular tempera- The precipitated burkeite, havin a ratio of sodium carbonate to sodium sulphate less than unity, may be utilized, as before described, for the productionof sodium sulphate, cold sulphate liquor, and further quantities of hot carbonate liquor. The precipitated sal soda may be included obtained, in following steps, from the hot carbonate liquor and used for the final production of soda ash.

The foregoing sal soda precipitation from sulphate-carbonate mixtures containing sodium carbonate in excess of 50% of the sodium means of extracting sodium chloride from the raw material, as set forth for the case of production, must be applied in this instance. One of the preferred methods is the leaching of the sodium chloride therefrom, if such exists, by means of the cold sulphate liquor, the residue being employed as just described. Other means, such as water leaching, may be'employed according to the precepts of this invention.

The hot carbonate liquor, the foregoing treatment and precipitation of burkeite from any of the above examples, may be treated with ammonia to precipitate the carbonate content, or treated in any other preferred or desired manner. This hot carbonate liquor, being relatively free from sodium sulphate, is useful in many instances as a raw materialfor example, for the manufacture of caustic soda by the lime process. However, we prefer to take this hot carbonate liquor which may have a composition apresulting from proximating point G of Figure 3 for the particular temperature in question, and cool the same to a temperature considerably below that of the transition point of the monohydrate of sodium carbonate to the heptahydrate,.which in saturated sodium chloride solution is about 26 C. As the solution is cooled, the composition remains essentially constant along the line GH since the cooling causes the solution to become unsaturated with respect to burkeite and also with the monohydrate of sodium carbonate if the sobe recovered to advantage as a marketable 'drate, the solution On thez other hand, if the hot carpgoduct. n

nate liquor hfasbeen produced at a rela-- tively low temperature, then only a very small ore of sodium chloride may sai crop being too small in certain instances to pay to handle. In such case, it may be desirable to slightly dilute before cooling.

At point H, the solution becomes saturated with a higher hydrate of sodium carbonate. In the case of the particular condition chosen for illustration, the point H is-in the dekahydrate field at about C. Further cooling is carried on to, say, 5 C. which causes crystallization of sodium carbonate dekahyfollowing the composition line along curve H-J. The removal of water from the solution as combined water of crystallization of the sodium carbonate dekahydrate, tends to slightly concentrate the other soluble constitutents, such as sovantage in fmaybe ing and removal of the precipitated salt dium sulphate and chloride. At the point J, the solution has approached very closely to saturation with sodium sulphate dekahydrate and cooling is therefore stopped and the crop of sodiumcarbonate dekahydrate crystals removed. The liquor remaining is either discarded or further treated to recoverthe sodium chloride content. As previously set forth a portion of this mother liquor may be employed to adcase sodium carbonate monohydrate is to in the hot carbonate liquor production step.

Said concentration may cause the precipitaamount of. sodium chloride. This effect maybe neglected in cases where high purity of product is not of paramount importance. However, where a product of highest purity is desired, it is preferable to add to the solution sufiicient water to maintain therein any sodium chloride which would tend to precipitate in refrigerating to a low temperature.

This water may be added directly to thehot carbonate liquor in case no sodium chloride recovery is desired, or it added to said liquor after partial coolprior to the precipitation of the main crop of sodium carbonate. In any case, the quantity of water added for this purpose is a small fraction of the total weight of the solution. In the foregoing illustration the I sodium chloride precipitated byvcooling to about 20 C. is allowed to settle and removed from the liquor. To the clear liquor we add be precipitated, I

be leached fromthe salt residues- 4-5% of fresh water by weight prior to the step of refrigerating to about 5 C.

Referring to the specific example of the hot carbonate liquor obtained by preci itation of burkeite from such as Owens La e brine and assuming that sodium tion is not desirable in th's instance, to 1562 pounds of this liquor we add 110 pounds of water and then cool the mixture from C. to approximately 15 C. t which point it reaches saturation with sodium carbonate dekahydrate. V

A further cooling to approximately 0 C. caused a separation of about essentially pure sodium carbonate dekahydrate equivalent to about 110 pounds of anhydrous sodium carbonate. The remaining solution had approximately the following composition:

Pounds 300 pounds of chloride produc- NaCl Other salts 92 Water 920 into the constituent parts o't'such, merely by subjecting the same to solution and temperature changes, the process may be economically operated for the recovery of sodium sulphate, sodium carbonate and sodium chloride of high degree of purity, also from mixtures containing considerable other impurities, such as borates and potassium salts.

The sal soda produced bysuitable refrigeration of hot carbonate liquor, produced by any of the aforementioned means, may be filtered ofi on a continuous vacuum filter or other suitablee uipment. A slight wash of cold water may e applied for displacing the adhering liquor. This product is suitable for the market as such; but, due to market conditions, freight rates, etc., it is preferable in the case of Glauber salt.

therefrom, as

sal soda may For example,

be dissolved in a no I minimum of water at or near the temperature of maximum solubility, about 35 C. From onate monohydrate this point, sodium carb may be produced by any one of the methods described above for the production of anhydrous sodium sulphate from Glauber salts. As in the foregoing example, in keeping wit the precepts of this invention, we prefer to produce the lesser hydrated carbonate by means employing the least expenditure of energy, i. e. by the saltingout method.

For example, to 1463 pounds of pure, wet

V solution may be 6" and then exceeding sal soda, containing 532 pounds of Na CO there is added 160 pounds of water, providing a total of 1623 pounds of solution, when the mixture is brought to 35 C. The resulting filtered or settled for the removal of insoluble matter, if desired. To this solution there is added 250 pounds of s o-v dium chloride, and the mixture stirred and maintained at 35 C. for about a half hour. The solid residue, comprising 320'pounds of N a CO .H O, on a dry basis, may be' recovered from the solution by means of a filter or centrifugal machine. A slight wash with warm water serves to displace the adhering monohydrate may be marketed as such, or it may be dried for the removal of the greater portion of thewater of crystallization, pro: ducing approximately 275 pounds of dense soda ash of high-purity. f End liquor from this: salting-out process may be returned to the hot carbonate liquor for further-recovery of the sodium carbonate content thereof, thereby providing a satisfactory overall yield value for the combined process. 7

As in the case of anhydrous sodiumsulphate manufactured from Glauber salt, impure sodium chloride may be employed for saturating the sodium carbonate solution. y sodium carbonate therein contained is added to the yield of sodium carbonate mono- 'ydrate produced. Sodium sulphate, if not exceeding approximately 12% of the sodium chloride contentof the impure salt employed. remains in solution at 35 contaminate the precipitated carbonate. The efiiciency of the above process may be further increased by decreasing the quantity of water employe for dissolving the sal soda, in which case the amount of sodium chloride employed is adjusted so as to produce the desired degree of saturation with respect to the same.

As in the case of Glauber salt conversion, a higher temperature of saturation with sodium chloride, say 7 fi -100 C. results in a more complete bonate monohy ate from the solution.

e the particular processes herein described are well adapted to carry out the objects of the presen't'mvention, it is to be understood that various modifications and changes maybe made without departing from the principles of the invention, and the invention includesjall such modifications and changes as come within the scope of the appended claims.

\ We claim sodium sulphate complexes which comprises, bringing the salts to saturation in water at a temperature below the transition point of -=Gla11ber salt to anhydrous sodium sulphate the saturation point of the solution,

liquor. The 320 pounds: of sodium carbonate bringing the salts solid phase,

sodium G. and does not sodium recipitation of sodium car-' sulphate as Glauber tion nearly saturated with respect to burkeltc 1. A process of treating sodium carbonateincreasing the percentage of.

sodium carbonate in the solution while form- 1 ing a solid 'phase'of Glauber salt.

2. A process of treating sodium carbonatesodium sulphate complexes which comprises, bringing'the salts to saturation in watenfree of sodium chloride, ata tem erature below the transition point of Glau r salt to anhydrous sodium sulphate and then exceeding the saturation point of the solution, increasing the percentage of sodium carbonate in 3. A process of treating sodium carbonatesodium sulphate complexes which comprises, to saturation in water at a temperaturebelow the transition pointjof Glauber salt to anhydrous'sodium sulphate, and then providing an excess of the complex in contact with the solution so as toincrease the sodium carbonate concentration of the solution while providing Glauber' salt as a the excess complexprovidedbe ing sufficient to bring the composition of the solution to substantially the' solubility at said temperature of sodium" carbonate dekahydrate. 4. A process of treating sodium-carbonatesulpliate complexes which comprises, bringing the salts to saturation in water at a temperature below the transition point of Glauber saltto anhydrous sodium sulphate,

'the'solution while forming a. solid phaseof Glauber salt.

and then providing an excess of the complex a in contact with the solution so as to increase the sodium carbonate concentration of the solution while providing Glauber salt .as a

solid phase, the excess complex added and the temperature of the solutionsuch as to bring the composition of the solution tosubstantially the transition point between burkeite,.Glauber alt and solid carbonate dekahydrate.

5. A process of treating sodium carbonate-r.

water to dissolve substantially all the sodium tlon point of Glauber salt to anhydrous sodium sulphate, crystallizingtheexcess sodium salt, and forming a soluand sodium carbonate dekahydrate.

v 6. 'A process of treating burkeite" which comprises, gesting burkeite with just suflicient water to 'dissolve'all of the sodium carbonate content at a temperature close to the tem erature of the transition point between bur eite, Glauber salt and sodium carbonate dekahydrate, while crystallizing out sodium,

sulphate salt, just suflicient burkeite ,bein digested to form a solution near the transition point between burkeite, Glauber salt and sodium carbonate dekahydrate.

7. Aprocess of treating sodium carbonate sodium sulphate complexes which comprises,-

sulphate complexes which comprises,

digesting the solid-salts with justsufiicient heating the heating a solution of the sodium carbonatesodium sulphate complex at a temperature above the transition int of sodium carbonate and sodium sulp ate to the double salt burkeite, which solution of the com lex contains a greater ratio of sodium ear onate to sodium sulphate than the ratio of these salts in burkeite, and then adding sodium chloride to the solution in suflicient quantities to depress the solubility of burkeite in the solution and cause the solution to precipitate burkeite and materially increase its carbonate to sulphato ratio. 7

8. A process of treating sodium carbonatesodium sulphate complexes which comprises,

solution of the complexes, containing greater ratio of carbonates to sulhates than the ratio of these constituents in urkeite, to a temperature substantially above the transition point of sodium carbonate and sodium glgliphate to the double salt burkeite, adding 'um chloride to the solution to nearly saturate the same therewith, and precipitating burkeite from the solution, the solution operated upon containing a ratio of carbonate to sulphate sufiiciently high so that such precipitation of burkeite brings the composition of the solution nearly to saturation with sodium carbonate monohydrate.

9. A process oftreating sodium carbonate- 7 sodium sulphate complexes which comprlses,

heating a solution of the complexes to a ternperature substantially above the transition point of sodium carbonate and sodium sul-- phate to the double salt burkeite, which solution contains a carbonate-sul hate ratio substantially correspo ing to t e ratio of carbonate to sulphate of a solution at said transition point, and substantiallysaturating the solution withsodium chloride thereby precipitating burkeite.

' burkelte in just suflicient p 10. A process of treating sodium carbonatesodium sulphate complexes which comprises,

heating a solution of the complexes to a temperature substantially above the transition point of sodium carbonate and sodium sulphate to the double salt burkeite, which solution contains a carbonate-sul hate ratio substantially corresponding to t e ratio of'carbonate to sulphate of a solution at said tran'sisaturating the A tion point, and substantially solution with sodium chloride thereby precipitating burkeite, the saturation of the solution with sodium chloride being efiected by adding mixed salt of sodium chloride and substantially all of the sodium chloride con tent of the mixed salt is dissolved in saturating said solution. g

11. A process of treating burkeite-containing sodium chloride which comprises, first leaching from the burkeite its sodium chloride content, then digesting the remaining solid salt with just su cient water to dissolve all of the sodium carbonate and form a solusubstantially at saturating the same quantities so that tion having I approximately the carbonate transition point between between sodium carbon-- burkeite, the temperature being maintained a the temperature of said transition point, while crystallizing the excess sodium sulphate, then heating the solution at a temperature substantially above the said transition point and substantially saturating the same with sodium chloride thereby precipitating burkeite.

13. A process of treating sodium carbon-- ate-sodium sulphate complexes which comprises, digestin the comp exes with sufiicient water to disso ve essentially all of the. sodium carbonate content form a solution of substantially the composition of the transition point between sodium carbonate, sodium sulphate and the double salt burkeite, the temperature being maintained substantially at the temperature of said transition point, while crystallizing the excess sodium sulphate, then heatin the solution to a temperature substantial y above the said' transition point and substantially with sodium chloride, thereby precipitating burkeite, and employing these arated burkeite as a sodium carbonate-so um sulphate complex in said digesting operation.

14. A process of treatin sodium carbonate-sodium sulphate comp exes prises, digesting the complexes with suflicient water to dissolve essentially all of the sodium carbonate content of the complex and form a solution of substantially the composition of the transition point between sodium carbonate, sodium sulphate and the double salt burkeite, the temperature being maintained substantially at the temperature of 'said transition poi' t, while 0 stallizing the excess sodium sulphate,-then heating the solution to a temperature substantiallyabove the said transition point and substantially satmating the same with sodium chloride thereby precipitating burkeite, and employing the separated burkeite as a sodium carbonatesodium sulphate complex in said digesting op- I solution being saturated with so j of the complex and which com-- a Ill ' phate,

chloride at an elevated saturate said solution so that its burkeite content remains undissolved.

15. A process of recovering sodium sulphate from sodium carbonate-sodium sulphate complexes which consists in digesting the solid salts with suflicient water to just dis: solve essentially all of the sodium carbonate at a temperature below the transition point of Glauber salt to anhydrous sodium sulcrystallizing the excess sodium sulphate as Glauber salt, separating the said ((iirlauber salt from the solution, adding soof sodium carbonate and sodium sulpoint to the double salt, burkeite, sufiicient phate' sodium chloride being added to-essentiall saturate the solution, separating the 'precipltated burkeite from the solution, and returning said burkeite to provide solid salts insaid digesting operation.

16. A process of treating mixtures composed essentially of sodium carbonate-sodium sul hate and sodium-chloride which consists 1n caching the mixture with suflicient water to'dissolve essentially all the sodium chloride, separating the carbonate sulphate residue from the solution, digesting said residue with suflicient water to dissolve essentially all the.

sodium carbonate at a temperature below the transition point of Glauber salt to anhydrous sodium sulphate, crystallizing the excess sodium sulphate as Glauber salt, heating the solution and addin the'solid mixture of sodium chloride and urkeite in suflicient quantities to saturate the solution with chloride at a temperature above the transition point of sodium carbonate andsodium sulphate to burkeite, thereby precipitating .burkeite .from the solution, separating the mixture of undis solved and precipitated burkeite irom the solution, and returning said burkeite to the aforesaid cycle of opera tions.

' '17; A process of treating solutions contain- 1ng sodium carbonate and sodium sulphate in quantities sufiicient to allow precipitation of portions of said' salts in the form of burkeite by saturating said solutions with sodium temperature, which comprises bringing said solutions to saturation with sodium chloride at a temperature above the transition point of sodium carbonate and sodium sulphate to burkeite, separating the precipitated-burkeite from the solut:on,.d1gest1ng said burkeite in just sufiicient water to dissolve essentially all... the sodium carbonate at atemperature below the transition point of Glauber salt to anhydrous sodium sulphate, crystallizing the excess sodium sulphate as Glauber salt, and then heating and saturating said solution withfsodium chloride as in the first mentioned. operation.

. 18. Aprocess of treating sodium carbonatesodium sulphate complexes which comprises,

chloride to the liquor and heating the liquor to a temperature above the transition the following cycle of operations,

heating a solution of the complex at a temperature above the transition point of sodium carbonate and sodium sulphate to the double salt burkeite, which solution of the complex ontains a greater ratio of sodium carbonate to sodium sulphate than the ratio of these salts in burkeite, then, adding sodium chloride to the solution in suflicient quantities to depress the solubility of burkeite in the solution and cause the solution to precipitate burkeite and materially increase the ratio of carbonate to sulphate, and finally precipitating sodium carbonate dekahydrate from the solution.

19. A process oftreating sodium carbonatesodium sulphate complexes which comprises, heating a solution of the complex containing a greater ratio of carbonates to sulphates than the ratio of these constituents in burkeite to a temperature substantially above the transition point of sodium carbonate and sodium sulphate to the double salt burkeite, adding sodium chloride to the solution to nearly and precipitating.

saturate the same therewith burkeite from the solution, the solution operated uppn containing a ratio of carbonate to sulphate sutficiently high so that such precipitation of burkeite brings the composition of the solution nearly to saturation wlth sodium carbonate monohydrate, and then cooling the solution to precipitate sodium carbonate dekahydrate. v

20. A process of treating sodium carbonate- -sodium sulphate complexes which comprises,

'following cycle of operations, digesting a complex of sodium carbonate-sodium sulphate within the Glauber salt field while precipitating Glauber salt and producing a solution near the composition of the transition point between sodium carbonate dekahydrate, Glauber salt and burkeite,'then heating the solution to a temperature substantially above the temperature of said transition point and saturating the solution with sodium'chloride to precipitate burkeite, and then cooling the solution and precipitating sodium carbonate dekahydrate.

22. A process of treating sodium carbonates'odium sulphate complexes which includes a complex of sodium carbonate-sodium sulphate Within the Glauber salt field while precipitating Glauber salt and producing a soludigesting Y tion near the composition of the transition int between sodium carbonate dekahydrate,

lauber salt and burkeite, then heating the solution to a temperature substantially above the temperature of said transition point and saturating the solution with sodium chloride to precipitate burkeite, then cooling the solution and precipitating sodium carbonate dekahydrate, the burkeite precipitated being recycled to a digesting operation.

23. A process of treating sodium carbonatesodium sulphate complexes which comprises,

heating a solution of complexes to a tempera ture substantially above the transition point of sodium carbonate and sodium sulphate to the double salt burkeite, which solution contains a carbonate-sulphate ratio substantially corresponding to the ratio of carbonate to sulphate of a solution at said transition point, substantially saturating the solution with sodium chloride, thereby precipitating burkeite,

, the saturation of the solution with sodium cooling t chloride being eiiected by adding a mixed salt of sodium chloride and burkeite in just sufilcient quantities so that substantially all of the sodium chloride content of the mixed salt is dissolved in saturating the said solution, and cooling the solution to precipitate the dekahydrate of sodium carbonate.

24. A process of treating burkeite containing sodium chloride and excess sodium carbonate which comprises, first leaching from the burkeite the sodium chloride and excess.

sodium carbonate content, then digesting the remaining solid salt with just suflicient'water to dissolve all of the sodium carbonate of the salt and form ,a solution having approximately the carbonate composition of a transition point between sodium carbonatesodium sulphate and the double salt burkeite, adding to said solution the solution formed by said leaching operation, heating and saturating the resulting solution with sodium chloride 'to precipitate burkeite, and cooling the solution to precipitate sodium carbonate dekahydrate.

25. A process of treating sodium carbonate-sodium sulphate complexes which comprises, digesting the complexes with sufiicient water to ssolve essentially all of the sodium carbonate, content of t e complex and form a solution of substantially the comsition of the transition point between soium carbonate, sodium sulphate and the double salt burkeite, the temperature being maintained substantially at the temperature of said transition point, while crystallizing the excess sodium 'sulphate,'then heatin the solution at a temperature substantially a ove phate'to the double salt the said transition point and substantially saturating the same with sodium chloride thereby recipitating burkeite, and then carbonate dekahydrate.

2 6. A process of treating sodium carbonchloride thereby e solution to precipitate sodiumate-sodium sulphate complexes which comprises, digesting the complexes with sufficient water to issolve essentially all of the sodium carbonate content of the complex and form a solution of substantially the compositiomof the transition point between sodium carbonate, sodium sulphate and the double salt burkeite, the temperature being maintained substantially at the temperature of said transition point,.while crystallizing the excess sodium sulphate, then heating the solution at a temperature substantially above the said transition point and substantially saturating the same with sodium chloride thereby precipitating burkeite, emplo ing the separated burkeite as a sodium car onate-sodium sulphate complex in said'digestingoperation, and then cooling the solution to precipitate sodium carbonate dekahy drate.

27. A process of treating sodium carbonate-sodium sulphate complexes which comprises, digesting the complexes with suflicient Water to dissolve essentially all of the sodium carbonate content of the complex and form a solution of substantially'the composition of the transition point between sodium carbonate, sodium sulphate and the double salt burkeite, the temperature being maintained substantially at the temperature of said transition point, while crystallizing the excess sodium sulphate, then heating the solution 'to a temperature substantially above, the said transition point and substantially saturating the same with sodium precipitating burkeite, employing the separated burkeite as a sodium carbonate-sodium sulphate complex in said. digesting operation, the solution being saturated with sodium chloride by adding a mixed salt of sodium chloride and burkeite containing just sufiicient sodium chloride to substantially saturate said solution, its burkeite content remaining undissolved, and then cooling the solution to precipitate sodium carbonate dekahydrate.

28. A process of recovering sodium sulphate from sodium carbonate-sodium sulphate complexeswhich consists in digesting the. solid salts with suflicient water to just dissolve essentially all of the sodium carbonate at a temperature below the transition Glauber salt from the solution, adding sothe solution dekahydrate.

precipitate sodium carbonate 29. A cyclical process of treating mixtures of burkeite, sodium carbonate monohydrate, and sodium chloride which comprises-di esting burkeite in sufiicient water, substantially free of sodium chloride at a temperature below the transition point of Glauber salt, sal soda. and burkeite, to dissolve essentially all the carbonate therein while crystallizing the excess sulfate as Glanber salt and forming a solution essentially saturated with Glaubersalt and sal soda, separating the precipitated Glauber salt from the saturated liquor, heating the resulting clear solution to a temperature substantially above said transition point, bringing said solution into contact with said raw material containing burkeite, sodium carbonate monohydrate, and sodium chloride, the sodium chloride therein contained being not greater than that required for saturating the resulting hot solution, effecting dissolution of the sodium carbonate monohydrate present, bringing the solution to substantial saturation with sodium chloride while dissolving from the solid residue substantially all sodium chloride, thereby forming a hot solution essentially saturated with sodium chloride, burkeite, and sodium carbonate monohydrate, separating the solid residue from the hot solution and returning said residue to the digestion operation in water at a temperature below said transition point, cooling the resulting clear solution to the point of precipitating a hydrated sodium carbonate, separating sodium chloride so precipitated, adding water to prevent further deposition of sodium chloride, and then refrigerating the resulting clear solution to precipitate sodium carbonate dekahydrate and separating said'carbonate from the refrigerated solution.

30. A process of treating solutions containing sodium carbonate and sodium sulphate in quantities suflicient to allow pre cipitation of portions of said salts in the form of burkeite by saturating said solutions with sodium chloride at an elevated tem erature, which comprises adding sodium ch oride to said solutions at a temperature above the transition point of sodium carbonate'and so dium sulphate to burkeite, separatingthe precipitated burkeite from the solution, digesting said burkeite in just suflieient water to dissolve essentially all the sodium carbonate at a temperature below the transition point of Glauber salt to anhydrous sodium sulphate, crystallizing the excess sodium sulphate as Glauber salt, then heating and saturatin said solution with sodium chloride as in t e first mentioned operation, and then cooling the'solution to precipitate sodium carbonate dekahydrate.

31. A. process of separating sodium carbonate-sodium sulphate complexes which comprises the following cycle of operations: dissolving a complex of sodium carbonate and sodium sulphate in such proportions of sodium carbonate and sodium sulphate and at such temperature that the resulting solution becomes saturated with Glauber salt before complete solution of the complex and Glauber salt is precipitated while the remainder of the complex is dissolved, then precipitating burkeite from the solution, precipitating sodium carbonate from the solution, and recyclin r the burkeite to the first operation.

32. process of treating sodium carbonatesodium sulphate complexes which comprises, digesting the complex in water until a solution is formed saturated with respect to one of the components, then continuing to digest the complex with said solution while enriching the solution in one of the components, and precipitating the other component as a hydrated salt. p 1

33. A process of treating sodium carbonate-sodium sulphate complexes which com.- prises, bringing the salts to saturation in water free of sodium chloride at a temperature close to the temperature of transition between Glauber salt, sal soda and burkeite, and continuing to digest the complex, precipitating one component as a hydrated salt while enrichin the solution in the other component, sufilcient complex and water being employed to form a solution with the composition approximating the composition of a solution at the transition point between Glauber salt, sal soda and burkeite.

34. A process of treating sodium carbonate-sodium sulphate complexes which comprises, bringing the salts to saturation in water free of sodium chloride at a temperature close to the temperature of transition between Glauber salt, sal soda and burkeite, and continuing to digest the complex, precipitating one component as a hydrated salt while enriching the solution in the other component, sufiicient complex and water being employed to form a solution with the composition approximating the compositionof a solution at the transition point between Glauber salt, sal soda and burkeite, heating the solution to a temperature substantially above the temperature of said transition point and essentially saturating the solution with sodium chloride dium carbonate and sodium sulphate containing sodium chloride, and uncombined sodium carbonate while bringing the solution essentially to saturation "with sodium chloride, thereby to precipitate burkeite excess sodium carbonate from said salt, bringthe burkeite and cooling the solution to pre.

ing the solution to essential saturation with respect to sodium chloride while precipitating burkeite, and separating the burkeite from'the solution.

37. Av process of treating sodium carbonate-sodium sulphate complexes which comprises,bringing a solution of sodium carbon- 6 ate and sodium sulphate to essential saturation with respect to sodium chloride to precipitate burkeite, separating the burkeite and cooling the solution to precipitate sodium chloride.

38. A process of treating sodium carbonate-sodium sulphate complexes which comprises, adding sodium chloride to a solution of sodium carbonate and sodium essentially saturate the solution with sodium chloride and precipitate burkeite, separating cipitate sodium chloride, the solution being cooled to saturation with sodium carbonate dekahydrate, separating the sodium chloridefrom the solution and further cooling the solution while precipitating the sodium carbonate dekahydrate. i

39. A process of treatin sodium carbonate-sodium sulphate comp exes which comprises, heating a solution of the composition corresponding substantially to the transition point between sodium carbonateand sodium sulphate and burkeite to a temperature sub stantially above such transition point and, then leaching with said solution a sodium 8111- phate-sodium carbonate complex containing an excess of sodium carbonate over that existing in burkeite, while brin 'ng the solution essentially tosaturation with sodium chloride soas to precipitate burkeite, whereby the excess sodium carbonate monohydrate in the leached salt brings the composition oi the'solution substantially to saturation with sodium carbonate monohydrate.

-10. A process of treatin sodium caifbonate-sodium sulphate comp exes which comprises, heating asolution of approximatel sulphate to.

substantially above the transition temperature of said transition point, then .digestlng a mixed salt of burkeite, sodium carbonate and sodium chloride with said solution until said solution is essentially saturated with sodium chloride while precipitating burke- 'ite, said mixed salt containing an excess of sodium carbonate over that which-will be dissolved by said solution, and adding water suflicient to dissolve said excess carbonate.

41. A process of treating sodium sulphatesodium carbonate complexes which consists in digestin excess 0 in burkeite and contains also sodium chloride with a solution of sodium carbonate and sodium sulphate which is thereby essentially saturated with sodium chloride from said such a complex which contains an sodium carbonate over that existing complex and precipitates burkeite, the com-v plex containing an excess of sodium carbon,-

ate over that which would be dissolved by said solution, adding suflicient water to the solution and complex to dissolve said excess sodium carbonate, removing the solution from the solid phase, and precipitating sodium carbonate dekahydrate therefrom.

42. A process of treating sodium sulphate carbonate complexes which comprises heat ing a concentrated solution of said complexes to a temperature substantially above the transition point of sal soda, Glauber salt and burkeite, said solution containing more sodium carbonate than sodium sulphate,

bringing the solution into-contact with impure sodium chloride while maintaining the mixture at elevated temperature thereby precipitating burkeite, adding water to dissolve sodium carbonate monohydrate from thesolid phase thereby forming a solution essentially saturated with respect toburkeite, sodium carbonate inonohydrate and sodium chloride and then separating the solid phase of burkeite from the hot'sludgeL Signed at Trona, California this 17th day of January, 1930.

WILLIAM. H. ALLEN. WILLIAM A. GALE. CHARLES F. RITCHIE.

the composition of a solution at the'transltion point between sodium carbonate and sodium sulphate and burkeite to a temperature 

